Synthetic resin and method of producing the same



- hol with Patented Mar. 5, 1935,

I PATENT OFFICE srnrnn'rro RESIN AND METHOD OF 1 PRODUCING THE- SAME Ernest G. Peterson,

- Hercules Powder Company,- a corporation of Delaware No Drawing.

Application Serial No. 686,439

Wilmington, Del., assigrior to Wilmington, DeL,

' 38 Claims. (01. zoo-s) and method of producing and more relates to a new form method for its production.

particularly of synthetic resin and droxyl groups the three groups will My invention broadly involves a reaction product of a polyhydric alcohol and an acidic resin formed from a terpene hydrocarbon possessing no conjugated system of double bonds and maleic anhydride, the product being characterized by the fact that the polyhydric alcohol is only partially combined with the acidic resin. In carrying out my invention the partial com-- bination of the polyhydric alcohol with an acidic resin formed from a terpene hydrocarbon possessing no conjugated system of double bonds and maleic anhydride may ways with the productionof varying and widely Thus, the partial combination may be effected in various 1- products possessed differing characteristics.

plished by causing the reaction] between a polyhydric alcohol and the acidic resin to be stopped prior to complete combination oij the polyhydric alcohol with the acidic resin or by. partially combining the polyhydric alcohol with-some substance other than the acidic resin.

J l In carrying out my invention the reaction between a polyhydric alcohol the described above may be resin by any desired, manipulation, ably will be effected reaction in the presence will operate. to either cause less reactive and thus the acidic resin readily terminable complete combination therewith, or

acidic resinstopped prior to comalcohol with the acidic but preferthrough carrying out the or some substance which the alcohol to be renderits reaction with prior to its which will itself react with the alcohol and with which the alcohol will partially combine. Alternatively, the

polyhydric alcohol may tial combination with some he pretreated for its parsuitable substance and finally reacted with the acidic resin for its partial combination therewith. or,

where the re-' action of the alcohol with the acidic resin' is stopped before complete combination the acidic resin,

of the alcothe product may be reacted with a substance which will satisfy the remaining reactive portion of the alcohol.

As generally illustrative of the carrying out of my invention where, for example,

the product desired involves the reaction of glycerol with an acidic resin and the reaction is carried out in the presence of a substance enabling the reaction to be readily prise glycerol molecules with which terminated, the product will comhave combined acidic resin molecules, to an extent, how- Mylinventionrelates to a resinous composition s; ever, insuficient to fully which will enable satisfy the reactive capacity of the glycerol molecules. In other words, in the cas of glycerol having three hynot be completely combined with the acidic resin.

On the other hand, where, for example, for the production of a desired product glycerol and the acidic resin are reacted in thepresence of a substance which itself will combine with the glycerol, the product will involve glycerol molecules combined partially with acidic resin molecules and partially with molecules 01 theother sub: stance used. In other words, the hydroxyl groups of the glycerol will be combined with the acidic groups of the resin inpart and other substance used.

Thus, in accordance with my invention it will now be understood that the novel product contmplated by me involves a polyhydrio alcohol partially combined with an acidic resin formed from a terpene hydrocarbon possessing no conjugated system 01 double bonds and maleic anhydride and that the novel method embodying my invention involves more particularly effecting the partial combination of a pqlyhydric alcohol and the acidic resin in the presence of a substance fore complete combination without itself entering into the reaction or which entering into thereaction will partly combine with the alcohol, which substances 1 shall hereinafter refer to as modifying agents.

The synthetic resins embodying my invention will differ widely in their physical characteristics and-in theiradaptability for various uses depending upon the particular polyhydric alcohol used and the method followed in their production. Thus; they may be hard or soft bodies or may be viscous liquids and will be adaptable for. use for various purposes, as for example, in substitution for gums or resins in cquers, varnishes, and i the likei The acidic resins iofthe formation of these synthetic resins embodying this invention are formed by the reaction of a terpene hydrocarbon ,with inaleic anhydride, The resinous esters embodying this invention may be produced by the esterification of an acidic resin formed by the reaction of a terpene hydrocarbon, characterized by the fact that'it does not have any conju ated system 01' double bonds, and maleic anhydridaor equivalently maleic acid, in the presence or heat, for example, as disclosed in my, application ior United States patent, Serial No. 683,627, filed August 4,1933. W

termination of the reaction be- The term terpene hydrocarbon as used throughout this specification refers solely to those terpene hydrocarbons having the formula CroHrc, often 'knownas true terpenes" or terpenes proper.

Generally speaking, the, terpene hydrocarbons not having any conjugated system of double bonds comprise alpha-pinene (b.p. about 153-151" C.). beta-pinene (p.b. about 160-168 C.), dipentene (b.p. about 170-178 C.)' and its optical isomers, as diand l- -limonene, andterpinolene (b.p. about 183-185 C.)

The acidic resins may be prepared, as is more fully disclosed in the application above referred to, by heating a terpene hydrocarbon possessing no conjugated system of double bonds, such as, terpinolene, dipentene, alphaor beta-pinene, with maleic anhydride. The reaction may be effected in any suitable manner, but will preferably be carried out by refluxing the terpene hydrocarbon with the maleic anhydride. It is desirable to use an excess of terpene hydrocarbon, which can be recovered unchanged by distillation upon completion of the reaction.

For reaction with the acidic resin 1 may use any suitable polyhydric alcohol, as for example, glycerol, polyglycerol and a glycol, as ethylene glycol, propylene glycol, diethylene glycol, or the like, etc., substituted polyhydric alcohols, such as, glyceryl monoacetate, glyceryl monoethyl ether, glyceryl monochlorhydrin, etc. The, polyhydric alcohol may be in admixture with a monohydric alcohol, such as ethyl, methyl, butyl, bornyl, fenchyl, abietyl alcohol, etc. As the modifying agent I may use various substances, as for example, an organic acid, a natural resin or resin acid, as rosin or abietic acid, manila copal, congo copal, etc., a vegetable or animal oil,

as linseed oil, China-wood oil, castor oil, fish oil, etc., or the fatty acids derived therefrom, fatty acids, such as stearic acid, oleic acid, etc., and dibasic acids, such as succinic, maleic acid, tartaric acid, adipic acid, sebacic acid, etc.

It will be understood that I contemplate the use of operable equivalents for the polyhydric alcohols mentioned and for the several modifying agents mentioned.

In proceeding in accordance with my invention for the production of a synthetic resin, for example, a mixture of about parts by weight of terpinolene-maleic anhydride, 75 parts of rosin (acid number 180) and 46 parts of glycerol are heated together at a temperature of about 210 C. for about'seven hours and .the temperature then raised to about 250 C. and the heating continued for about three hours. The treatment may be carried out in any suitable form of apparatus. During the heating considerable foaming will be noted and it is, therefore, desirable, as indicated above, to heat for a period at the lower temperature and to raise the temperature only when the reaction is nearly completed.

The synthetic resin prepared as above described will comprise glycerol partially combined with terpinolene-maleic anhydride and partially with abietic acid of the rosin, which, as will be understood, is capable of reacting with the glycerol and does react in the preparation of the resin preventing complete combination of the glycerol with the terpinolene-maleic anhydride.

.In place of terpinolene-maleic anhydride, dipentene-maleic anhydride, or alphaor. betapinene-maleic anhydride may be used in the example given above in equivalent amount The synthetic resin prepared as indicated wilt be found to be of a very light color, very clear and transparent, to have an acid number of about 16 and a softening point of about C. The synthetic resin will be found to be soluble in various known ester solvents and to be soluble in acetone, etc. The synthetic resin will be found to be only slightly soluble in alcohol and hydrocarbon solvents.

As a further illustration, for example, 330 parts by weight of rosin (A. N. 170) are dissolved in 234 parts'of terpinolene-maleic anhydride by heating, and 115 parts of glycerol are added. The mixture is gradually heated to a temperature of 270 C. and maintained at that temperature for approximately '7 hours. Agitation may be employed but is not absolutely essential since the evolution of water vapor serves to keep the mixture well stirred. The excess of glycerol is removed by applying a vacuum to the resin while in the heated condition. The product will comprise glycerol partially combined with terpinolene-maleic anhydrideand partially with abietic acid.

-In 'place of terpinolene-maleic-anhydride, dipentene-maleic anhydride, or alphaor betapinene-maleic anhydride may be used in the example given above in equivalent amount.

By theabove procedure a variety of esters having various characteristics and adaptable for various purposes, as for use in varnishes, lacquers, japans, paints, as substitutes for hard rubber and various other plastic articles, ,films, etc., maybe prepared by varying the proportions of rosin and of terpene-maleic anhydride used with resultant variation in the proportionate combination of abietic acid and of teprene-maleic anhydride with the glycerol.

As a further illustration, for example, 177 parts by weight of terpinolene-maleic anhydride, and 165 parts rosin (A. N. 1'70) are heated together at about C. to form a homogeneous solution, and 77 parts of ethylene glycol are then added. The mixture is heated at the boiling-point of the solution approximately 210 C., for about 8 hours. The excess glycol may be removed at the completion of the reaction by applying'a vacuum. The product will involve ethylene glycol partially combined with terpinolene-maleic anhydride and partially with abietic acid.

In place of terpinolene-maleic anhydride, dipentene-maleic anhydride, or alphaor betapinene-maleic anhydride may be used in the example given above in equivalent amount.

And as will be understood resins having various desirable characteristics and adaptable for vari ous purposes may be prepared by the above indicated procedure with the use as the modifying agent of various acidic gums, as congo or manila copal, etc., in place of rosinand the use of another polyhydric alcohol, as polyglycerol, ethylene oil or an acid derived therefrom as a modifying agent, for example, about234 'parts by weightof terpinolene-maleic anhydride and 56 parts of, for example, raw linseed oil are heated together until a homogeneous solution is produced, then about 62 parts by weight of glycerol is added and the tion of the reaction partially reactive generally, will glycerol with lacquers though mixture heated to a temperature of about 200 C. until the evolution of water vapor has ceased, indicating completion of the reaction. Complewill usually require about 9 to 10- hours where the heating is at 200 C., or the required period may be shortened somewhat by using a slightly higher temperature.

In place of terpinolene-maleic anhydride,

dipentene-maleic anhydride, or alphaor betapinene-maleic anhydride may be used in the example given above in equivalent amount.

The product produced as above described, using linseed oil, will compriselargely glycerol partially combined with terpinolene-maleic anhydride and or uncombined, that is to say, a portion of a hydroxyl group of the glycerol or one or more of-the groups will be uncombined with terpinolene-maleic anhydride though at the temperature used there may be some decomposition of the linseed oil resulting in the freeing of the fatty acid of the linseed oil which, insofar as such may be freed may combine with the por- 1310B ofthe glycerol uncombined with the terpinolene-maleic anhydride. The presence of the linseed oil, however, will operate to enable the reaction between the glycerol and the terpinolenemaleic anhydride to be terminated prior to complete combination of the terpinolene-maleic' anhydride with the glycerol and hence the product will be characterized by the fact that the glycerol molecules are not completely combined with terpinolene-maleic anhydride though the uncombined portions of the glycerol molecules may be in whole or in part combined with the fatty acid of linseed oil, or may be in whole or in part reactive.

The synthetic resin be soluble in acetone,

produced will be found to toluol and ester solvents of flexibility, to be largely resistant to water, to satisfactorily harden at ordinary temperatures by the absorption of oxygen and to lend itself desirably for various uses such, for example, as in the preparation of varnishes, lacquers and enamels.

As a further illustration, for example, 1053 partsbyweight of terpinolene-maleic anhydride are heated with about 252-,parts of castor oil until a homogeneous solution results, then about 166 parts by weight of glycerol are added and the mixture heated at 215-220" C. until the evolution of water vapor has ceased indicating completion of the reaction. The castor oil will operate in much the same manner as does linseed oil, namely, it will enable the reaction between the glycerol and the terpinolene-maleic anhydride to be terminated before complete combination of the terpinolene-maleic anhydride and with such combination with the glycerol and the fatty acid of castoroil as may result from the freeing of the fatty acid through decomposition of the oil at the temperature used. The resultant resin will be found to be a light yellow in color, very clear and very tough, to be soluble in acetone and in'ester solvents, to soften at approximately 100 C. and to be compatible with nitrocellulose, rendering it desirable for use in nitrocellulose it will be foundto have various other uses, as for example, in varnishes, etc.

In place of terpinolene-maleic anhydride, dipentene-maleic anhydride or alpha- 01 betapinene-maleic anhydride may be used in the example given above in equivalent amount.

As a further illustratio for example, 351 parts -by weight of terpinolene-maleic anhydride are ,mately 6 hours. The

'pentene-maleic anhydride,

be found to possess a high degree dissolved in 284 parts raw linseed oil, the mixture heated to 150 C. and 92 parts of glycerol added. This mixture isthen heated for eight hours at a temperature of 220 C. pale yellow viscous liquid.

' In place of terpinolene-maleic anhydrlde, dior alphaor beta-' pentene-maleic anhydride, pinene-maleic anhydride may be used in the example given above in equivalent amount.

The resin will involve glycerol partly combined with terpinolene-maleic anhydride and partly uncombined or combined with the acid of linseed oil insofar as such may be freed thro h decomposition of linseed oil at the tempera used.

As has been indicated syntheticflresins embodying my invention may be produced by the use of fatty acids derived from vegetable or animal oils. Thus, for example, for the preparation of a synthetic resin embodying my invention 234 parts by weight of terpinolene-maleic anhydride are heated with 283 parts of the mixture of fatty acids produced by the'saponiflcation' of linseed oil and technically known as linseed fatty acids" to form a homogeneous solution; To the hot solution 92 parts of glycerol are added andthe mixture is heated at a temperature of 220 C. for approxitemperature is then raised to 250 C. for two hours. out in a vessel of such shape and construction that air may be excluded from the reaction mixture, as it is necessary to prevent oxidation of the fatty acids. For example,'carbon dioxide, or nitrogen gas may be passed into the vessel during the heati118.

In 1 place of terpinolene-malei'c anhydride, di-

pinene-maleic anhydride may be used in the example given above in equivalent amount.

Where the resin is produced by reacting the acidic resin and a polyhydric alcohol in the pres ence of afatty acid derived from a vegetable or animal oil, the resin product will involve essentially, the polyhydric alcohol partially combined with the acidic resin and partially combined with the fatty acid used. As a-further illustration, for example, 293 parts by weight of terpinolene-maleic anhydride and 142 parts of the fatty acids obtained by the saponification of China-wood oil are heated for a few minutes to form a homogeneous solution and then 92 parts of glycerol are added, This mixture is heated in a closed vessel at a temperature of 215- 220 C. for 5 to 6 hours in an inert atmosphere. The resin resulting is a transparent, light yellow solid. The resin will comprise essentially glycerol preciably and prevents the formation of insoluble gels in many cases. Where the reaction is carried on in the presence of rosin as well as of a fatty acid, the resin product will involve the polyhydric alcohol partially combined with the synthetic acidic resin, with the fatty acid and with abietic acid. V

As a further illustration, for example, 234 parts by weight of terpinolene-maleic' anhydride, 165 parts rosin (A. N. 170) and 146 parts of the fatty of alphaor beta-- The resin produced is a The reaction is carried uct will involve glycerol partially combined with terpinolene-maleic anhydride and partially with the fatty-acid derived from linseed oil, and with abietic acid.

In placeof terpinolene-maleic'anhydride, di-- pentene-maleic anhydride, or alphaor betapinene-maleic anhydride may be used in theexample given above in equivalent amount. The resins produced as above from unsaturated fatty acids may be further heated with a. drying oil such as China-wood oil to give an improved composition. For example, the resin as described, produced with the fatty acids obtained by saponification of China-wood oil may be heated with 50% of its weight of China-wood oil to give an improved composition having excellent water resistance.

As a further illustration, with the use, for example, of a dibasic acid, for example, 92 parts of glycerol are heated with 2l1'parts of terpinolenemaleic anhydride and 71 parts of, for example,

succinic acid at a temperature of 180-200 C. for about 15 hours. Completion'of the reaction may be noted by the fact that a cooled sample is not sticky. The resin produced will involve glycerol partially combined with 'terpinolene-maleic anhydride and partially combined with succinic acid. The resin product may be improved for various uses by further heating, as for example, by heating at a temperature of about 100 C. for a period of 24 hours and heating at a higher temperature; say 150-200 C. for a period of say 15-24 hours.

In place of terpinolene-maleic anhydride, dipentene-maleic anhydride, or alphaor beta.- pinene-maleic anhydride may be used in the example given above in equivalent amount.

It will be understood that the synthetic resins in accordance with my invention may-be prepared by varicus procedures differing from those described above by way of illustration, that is to say various proportions of acidic resin, of polyhydric alcohol and modifier may be used as well as various temperatures and times of-treatment, depending upon thesubstances usd.- As has been indicated, any suitable form of apparatus may be usedand the procedure may be carried out under various pressureconditions as may be desirable, depending upon the substances reacted.

It will also be understood that if desirable the reaction may be promoted through the use of catalysts, as for example, basic materials, such as calcium oxide or zinc oxide, or the like.

It will be clearly understood that I contemplate the production of the synthetic resins in accordance with myinvention by the use of an acidic resinformed from a terpene hydrocarbon possessing no conjugated system of double bonds and maleic anhydride, and of any suitable polyhydric alcohol including those specifically mentioned and operable equivalents therefor and with the use of any suitable modifying agent including those specifically mentioned and mixtures there-1 bonds and maleic anhydride, and partially reactive or partially combined with some other substance, the partial combination with a substance other than the acidic resin being accomplished simultaneously with the partial combination with the acidic resin or being effected prior to or subdrying oil, semi-drying oil or non-drying oil, as

perilla oil, soya bean oil, China-wood oil, fish oil, castor' oil, etc. or the corresponding fatty acids may be used in place of linseed oil as the modifying agent.

It will be understood that where in the claims appended hereto the term "polyhydric alcohol" is used, such is intended to embrace and include "substituted polyhydric alcohols as equivalents within the scope of this invention.

WhatI claim and desire to protect by Letters Patent is:

1. A reaction product of a polyhydric alcohol and an acidic resin formed from a terpene hydrocarbon of the formula C1oH1e and possessing no conjugated system of double bonds and maleic anhydride, characterized by the fact that only apart of the hydroxyl groups of the polyhydric alcohol are combined with the acidic resin.

*2. A reaction product of a polyhydric alcohol and terpinolene-maleic anhydride, characterized by the fact that only a part of the hydroxyl groups of the polyhydric alcohol are combined with the terpinolene-maleic anhydride.

3. A reaction product of a polyhydric alcohol, an acidic resin formed from a terpene hydrocarbon of the formula ClOHlG and possessing no conjugated system of double bonds and maleic anhydride, and a carboxylic acid. j

4. A reaction product ofa. polyhydric alcohol, terpinolene-maleic anhydride and a carboxylic organic acid. v z 5. A reaction productof a polyhydric alcohol, an acidic' resin" formed from a terpene hydrocarbon of the formula CmHm and possessing no conjugated system of double bonds and maleic anhydride, and a resin acid.

6. A reaction product-of a polyhydric alcohol, terpinolene-maleic anhydride and a resin acid.

'7. A reaction product of a polyhydric alcohol, an acidic resin formed from a terpene hydrocarbon of the formula Ciel-I16 and possessing no conjugated .system of double bonds and maleic anhydride, and an aliphatic dibasic acid.

8. A reaction product of a polyhydric alcohol, terpinolene-maleic anhydride and an aliphatic dibasic acid.

'9. A reaction product of a polyhydric alcohol, an acidic resin formed from a terpene-hydrocarbon of the formula CioH1s and possessing no conjugat'ed system of double bonds and maleic anhydride, and abietic acid.

10. A reaction product of a polyhydric alcohol, terpinolene-maleic anhydride and abietic acid.

/ 11. The method of producing a synthetic resin which includes reacting together a polyhydric alcohol, an acidic resin formed from a terpene hydrocarbon of the formula CmHis and possessing no conjugated system of double bonds and maleic anhydride, and a carboxylic organic acid.

12. The method of producing a synthetic resin which includes reacting together a polyhydric alcohol, terpinolene-maleic anhydride and a carboxylic organic. acid.

13. The method of producin a synthetic resin no conjugated system of double bonds and maleic anhydride, and a resin acid.

14. The method of producing a synthetic resin which includes reacting together a polyhydric alcohol, terpinolene-maleic 'anhydride and a resin acid. V

15. The method of producing a synthetic resin which includes reacting together a polyhydric alcohol, an acidic resin formed from a terpene hydrocarbon of the formula C10H16 andpos'sessing no f conjugated system of double bonds and maleic anhydride, and an aliphatic dibasic acid.

16. The method of producing a synthetic resin which includes reacting together a polyhydric alcohol, terpinolene-maleic anhydride and an aliphatic dibasic acid.

17. A reaction product of a polyhydric alcohol, an acidic resin formed from a terpene hydrocarbon of the formula CinHrs and having no conju gated system of double bonds and maleic anhydride, and succinic acid.

18. A reaction product of a polyhydric alcohol, an acidic resin formed from a terpene hydrocarbon of the formula ClOHlG and having no con-' 'jugatedjsystem of double bonds land maleic anhydride, and a fatty acid.

19. A reaction product of a polyhydric alcohol,

an acidic resin formed from a terpene" hydrocarbon of the formula C10H16 and having no conjugated system of double bonds and maleic anhydride, and a fattyacid derived from linseed oil. I

20. A reaction product of a polyhydric alcohol, terpinolen'e-maleic anhydride and succinicacid. 21. A reaction product of a polyhydric alcohol, terpinolene-maleic anhydride and a fatty acid. 22. A reaction product of a polyhydric alcohol, terpinolene-maleic anhydride and a fatty acid derived from linseed oil. v

23.- The method of producing a synthetic resin which includes reacting together a polyhydric 'alcohol and an acidic resin formed from a terpene hydrocarbon of the formula CmHm and having no conjugated system of double bonds andmaleic anhydride, under conditions suchthat only a part of the hydroxyl groups of the polyhydric alcohol combine with the acidic resin.

24. The method of producing a synthetic resin whichincludcs reacting together a polyhydric alcohol and terpinolene-maleic anhydride under conditions such that only a part of the hydroxyl groups of the polyhydric alcohol combine with the terpinolene-maleic anhydride.-

25. The method of producing a synthetic resin which includes reacting together a polyhydric alcohol, an acidic resin formed from a terpene hydrocarbon of the formula CmHm and possessing no conjugated system of double bonds and maleic anhydride, and a fatty acid.

26. The method of producing a synthetic resin which includes reacting together a polyhydric alcohol, terpinolene-maleic anhydride anda fatty acid. I

27. A coating composition comprising a reaction product of a polyhydric alcohol, an organic carboxylic acid and an acidic resin formed from a terpene hydrocarbon of the formula CmHm and having no conjugated system of double bonds and maleic anhydride, and a solvent. v

,28. A coating composition comprising a reaccarboxylic acid and an acidic resin formed from .a terpene hydrocarbon of the formula CIUHlB and having no conjugated system of double bonds and maleic anhydride, a lacquer ingredient and a solvent.

29. A coating composition comprising -a reaction product of a polyhydric alcohol, an organic carboxylic acid and an acidic resin formed from a... terpene hydrocarbon of the formula C10H1s and having no conjugated system of double bonds and maleic anhydride, a varnish ingredient and a solvent.

30. A-coating composition comprising a reaction product of a polyhydric alcohol, an organic carboxylic acid and terpinolene-maleic anhydride, t; and a solvent.

31. A coating composition comprising a reaction product of a polyhydric alcohol, an organic carboxylic acid and terpinolene-maleic anhydride,

a lacquer ingredient and a solvent.

32. A coating composition comprising a reaction product'of a polyhydric alcohol, an organic carboxylic acid and terpinolene-maleic anhydride, a varnish ingredient anda solvent.

33. A reaction product of a polyhydric alcohol selected from the group consisting of glycerol and aliphatic glycols, and an acidic resin formed from a terpene hydrocarbon of the formula CioHis and having no conjugated system of double bonds and maleic anhydride, characterized by the fact that only a part ofthe hydroxyl groups of the polyhydric alcohol are combined with the acidic resin.

'34. A reaction product of a polyhydric alcohol selected from the group consisting of glycerol and aliphatic glycols, and terpinolene-maleic anhydride, characterized by'the fact thatonly a part of the hydroxyl groups of thepolyhydric alcohol are combined with the terpinolene-maleic anhydride I v 35. A reaction product of a polyhydric alcohol selected from the group consistingof glycerol and aliphatic glycols, an acidic resin formed from a terpene hydrocarbon of the formula ClOHlG and having no conjugated system of double bonds and maleic anhydride, and an organic carboxylic acid.

tion product of a polyhydric'alcohol, an organic 36. A-reaction product of a polyhydric alcohol selected from the group consisting of glycerol and ERNES G. PETERSON. 

